Note: Descriptions are shown in the official language in which they were submitted.
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OIL-SOLUBLE PLANT MICRONUTRIENTS
[0001] This application claims the benefit of U.S. Provisional Patent
Application
Serial Number 62/376,585, filed August 18, 2016, the entire disclosure of
which is
incorporated herein by reference
STATEMENT REGARDING FEDERALLY
SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable.
FIELD OF THE INVENTION
[0003] The present disclosure is directed to an adjuvant composition
comprising (a) a
substantially oil soluble micronutrient salt obtained from the reaction of a
metal-
containing compound and an organic acid and (b) an oil. The adjuvant
composition
may be combined with a pesticide, such as a water soluble pesticide, to form
an
agrochemical formulation for application on and delivery of micronutrients to
plants.
BACKGROUND OF THE INVENTION
[0004] Certain elements are required by plants in very small quantities for
their
proper nutrition. These so-called trace elements (also referred to as minor-
or
micronutrients) generally include boron, calcium, copper, iron, magnesium,
manganese, molybdenum, nickel, selenium and zinc. The shortage of one or more
of
these trace elements can affect the plant appearance and its productivity,
giving rise to
typical growth problems. Trace element deficiencies in plants are widespread
and
often occur in soils which contain adequate quantities of the trace elements
but in
forms unavailable to the plant. For example, the positively charged metal ions
are
frequently absorbed by soil particles, forming insoluble solid metal
hydroxides.
Because plants are not able to separate the metals from the hydroxides, the
trace
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elements are lost to them. Sometimes un-complexed metal salts are dissolved
and
sprayed directly onto the plants, allowing the plants to take them up through
vacuoles
or other foliar transport systems. Examples of these salts include zinc
sulfate,
manganese sulfate, sodium borate and ammonium molybdate. Uptake of these salts
is
inefficient and significantly higher concentrations must be applied to reach
the desired
levels of uptake, resulting in waste and potential off-target runoff. In
addition,
uncomplexed salts create significant tank-mix compatibility problems with
other
fertilizers or pesticides (especially herbicides such as glyphosate or the
auxins).
[0005] One solution is to deliver metal compounds to the plant in a
"protected" or
chelated form that are more readily absorbed into the plants via foliar or
root uptake
and resist forming insoluble hydroxides. Chelates generally comprise a metal
and a
ligand that holds the metal in a bioavailable form that a plant can use.
Examples of
such chelates include EDTA, EDDHA, DTPA and NTA. However, the use of these
synthetic chelates has significant drawbacks, such as high costs associated
with their
production, their potential negative interaction when combined with pesticides
(i.e.
deactivation of the micronutrient and/or pesticide) in an agrochemical
formulation,
and, more recently, concerns over the fact that they may folin byproducts that
persist
in the environment for extended periods of time. Accumulation in soil and
waterways
due to the recalcitrant nature of synthetic chelates may lead to a negative
impact on
the environment. Moreover, EDTA is such an efficient complexor of metal ions
that
it can compete with the plants for the metal ion, thus resulting in
inefficiencies in
metal ion delivery to the plant. EDTA can also form complexes with toxic heavy
metals in the soil or in runoff areas, resulting in enhanced transport of the
heavy
metals into plants or waterways.
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[0006] In addition, it has also been known to use citric acid or citrate salts
as a
chelating agents. However, the use of citrate has been found to not be
generally
acceptable due to inferior stability constants at pH's greater than 7 and the
rapid
biodegradation of citrate in the soil. Moreover, another drawback in relation
to use of
this compound is its corrosiveness and the damaging effect this can have on
equipment used in its delivery, especially if inadvertently mixed in high
concentrations.
[0007] Finally, it has been known to use aqueous solutions of insoluble forms
of the
micronutrients (ZnO, CuO, MnCO3, MgCO3, etc.). However, because these solid
micronutrients have such a low solubility in any solvent, they are not
efficiently taken
up by plants.
[0008] While the use of synthetic chelates, organic acids or aqueous solutions
of
insoluble forms of the micronutrients have become the standard accepted way of
providing micronutrients to plants on the thought that such agents were the
best
possible and most efficient compounds available, there is a need to develop
more
environmentally acceptable and effective compounds for use in the delivery of
micronutrients to plants.
SUMMARY OF THE INVENTION
[0009] The present disclosure provides an adjuvant composition comprising a
micronutrient salt and an oil. The micronutrient salt is obtained from the
reaction of a
metal-containing compound comprising boron, calcium, copper, iron, magnesium,
manganese, molybdenum, nickel, selenium, zinc or a mixture thereof, and an
organic
acid comprising a sulfonic acid, a carboxylic acid, a phosphorous acid, a
boric acid or
a mixture thereof wherein the organic acid has a sufficient number of carbon
atoms to
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render the micronutrient salt that is formed substantially oil soluble. The
adjuvant
composition may also comprise a surfactant and an auxiliary component(s).
[0010] The present disclosure also provides an agrochemical formulation
comprising
the adjuvant composition above and a pesticide. In particular aspects, the
pesticide
may be a water soluble pesticide, including but not limited to, glyphosate,
2,4-D,
dicamba and glufosinate.
[0011] The present disclosure also provides a method for killing, inhibiting
or
repelling a pest which includes contacting the agrochemical foimulation and
the pest.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The present disclosure provides an adjuvant composition comprising a
micronutrient salt and an oil. The micronutrient salt, particularly useful as
a fertilizer,
may be obtained by reacting (i) a metal-containing compound comprising boron,
calcium, copper, iron, magnesium, manganese, molybdenum, nickel, selenium,
zinc
or a mixture thereof with (ii) an organic acid comprising a sulfonic acid, a
carboxylic
acid, a phosphorus acid, a boric acid or a mixture thereof, where the organic
acid has
a sufficient number of carbon atoms to render the micronutrient salt that is
formed
substantially oil soluble. In some aspects the adjuvant composition is
substantially
free of a chelate. Surprisingly, it has been found the oil-soluble
micronutrient salt,
when added to an oil and optionally surfactant and auxiliary component(s), is
readily
emulsifiable into water and can be added to an agricultural spray tank with or
without
tank mix partners, such as other fertilizers and/or pesticides.
[0013] In addition, it has also been surprisingly found that the adjuvant
composition
of the present disclosure may be useful in agrochemical formulations for
enhancing
efficacy of the active ingredients, especially water soluble pesticides, in
the
agrochemical formulations. By "enhanced" it is to be understood that the
adjuvant
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composition comprising the substantially oil soluble micronutrient and oil of
the
present disclosure increases the performance of the active ingredients, for
example
water soluble pesticides, in agrochemical formulations (for e.g., a higher
activity of
the active ingredients for a given application rate, a lower application rate
with a
given effect, better uptake of the active ingredient by the target substrate,
and thus
advantages for a pre-emergence or post-emergence treatment, in particular the
spray
treatment of target substrates) as compared to agrochemical formulations that
do not
contain the adjuvant composition of the present disclosure. In particular,
it's known
that state of the art micronutrient salts (for e.g., manganese sulfate and
zinc sulfate)
interfere with and can deactivate water soluble pesticides, such as
glyphosate, 2,4-D,
dicamba and glufosinate. However, the substantially oil soluble micronutrient
salts of
the present disclosure are capable of being substantially dispersed in oil
allowing
them to be used with such pesticides without detrimental effects.
[0014] The following terms shall have the following meanings:
[0015] As used herein, the term "plant" includes reference to whole plants,
plant
organ, for e.g., leaves, stems, roots, plant tissue, seeds, and plant cells
and progeny
thereof. Plant cell, as used herein includes, without limitation, seeds, for
e.g., seed
suspension cultures, embryos, meristematic regions, callus tissue, leaves,
roots,
shoots, gametophytes, sporophytes, pollen, and microspores.
[0016] The term "micronutrient" means an element that is essential in trace
amounts
for plant growth. Examples of such micronutrients include, but are not limited
to,
boron, calcium, copper, iron, manganese, magnesium, molybdenum, nickel,
selenium
and zinc.
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[0017] The term a "pesticidally effective amount" refers to that amount of a
pesticide
which, upon application, either reduces the presence of pests or enhances a
plant's
resistance to a pest.
[0018] The term "target substrate" refers to sites underlying plant foliage
which are
the intended destination for the pesticide including, but not limited to:
natural ground
surfaces, such as soil and water (lakes, ponds, marshes, swamps, streams,
puddles,
etc.); artificial surfaces, such as pavement; a pest or a combination thereof.
[0019] The term "pest" generally includes insects, mites, ticks and other
arthropods,
disease agents, such as fungi, protozoa, bacteria and viruses. helminths,
nematodes
(roundworms), cestodes (tapeworms), platyhelminths (flatworms), trematodes
(flukes)
and other womis, sporozoan parasites, slugs and snails, and vertebrates such
as birds,
rodents or other vertebrates which can directly or indirectly injure or cause
disease or
damage in any plant or part thereof or any processed, manufactured or other
product
of the plant.
[0020] The term "chelate" means a coordination compound in which a central
metal
ion is attached by coordinate links to two or more nonmetal ligands, for
example,
EDTA or an amino acid, which form heterocyclic rings with the metal ion being
a part
of each ring.
[0021] The term "substantially free" means, when used with reference to the
substantial absence of a component in a composition, that such a component is
present, if at all, as an incidental impurity or by-product. In other words,
the
component does not affect the properties of the composition.
[0022] The phrase "substantially oil soluble" indicates that the indicated
component is
present in an oil phase in an amount of at least 95% by weight, or at least
97% by
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weight, or at least 99% by weight, or even at least 99.5% by weight, based on
the total
weight of the oil phase.
[0023] It shall be understood, that "organic acid" may also include metallic
salts of
the organic acid moiety. For example, in some aspects, the organic acid
includes a
sulfonic acid or metallic salt thereof, a carboxylic acid or metallic salt
thereof, a
phosphorus acid or metallic salt thereof, or a boric acid or metallic salt
thereof.
[0024] The term "comprising" and derivatives thereof are not intended to
exclude the
presence of any additional component, step or procedure, whether or not the
same is
disclosed herein. In order to avoid any doubt, all compositions claimed herein
through use of the term "comprising" may include any additional additive or
compound, unless stated to the contrary. In contrast, the term, "consisting
essentially
of' if appearing herein, excludes from the scope of any succeeding recitation
any
other component, step or procedure, excepting those that are not essential to
operability and the term "consisting of', if used, excludes any component,
step or
procedure not specifically delineated or listed. The term "or", unless stated
otherwise,
refers to the listed members individually as well as in any combination.
[0025] The articles "a" and "an" are used herein to refer to one or more than
one (i.e.
to at least one) of the grammatical object of the article. By way of example,
"an oil"
means one oil or more than one oil.
[0026] The phrases "in one aspect", "according to one aspect" and the like
generally
mean the particular feature, structure, or characteristic following the phrase
is
included in at least one aspect of the present disclosure, and may be included
in more
than one aspect of the present disclosure. Importantly, such phrases do not
necessarily refer to the same aspect.
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[0027] If the specification states a component or feature "may", "can",
"could", or
"might" be included or have a characteristic, that particular component or
feature is
not required to be included or have the characteristic.
[0028] According to one aspect, the present disclosure provides an adjuvant
composition comprising: a micronutrient salt obtained from the reaction of a
metal-
containing compound and an organic acid, and in some aspects, an organic acid
or salt
thereof; and an oil, wherein the organic acid (or salt thereof) has a
sufficient number
of carbon atoms to render the micronutrient salt that is formed substantially
oil
soluble. It has been surprisingly found the micronutrient salts of the present
disclosure are substantially oil soluble, and therefore exhibit enhanced
hydrophobicity
allowing them to be easily formulated into oil-based agrochemical formulations
for
application onto plants. Because of this enhanced hydrophobicity, additional
adjuvancy normally not present is built into these oil-based compositions
allowing the
micronutrient salts to penetrate/enter the targeted plant (for e.g. leaf
cuticle) more
quickly and efficiently than traditional water-soluble micronutrient salts.
Finally, in
contrast to state of the art water soluble micronutrient salts, the
substantially oil
soluble micronutrient salts will not interfere with or deactivate water
soluble
pesticides, such as glyphosate, 2,4-D, dicamba and glufosinate, and therefore
have the
capability to be successfully used in combination with these water soluble
pesticides
in various applications, such as in spray tank applications.
[0029] According to one or more aspects, the substantially oil soluble
micronutrient
salt is obtained from the reaction of (i) a metal-containing compound
comprising
boron, calcium, copper, iron, magnesium, manganese, molybdenum, nickel,
selenium,
zinc or mixture thereof and (ii) an organic acid comprising a sulfonic acid, a
carboxylic acid, a phosphorus acid, a boric acid or a mixture thereof.
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[0030] In one aspect, the metal-containing compound is a metal oxide, a metal
carbonate, a metal hydroxide or a mixture thereof of boron, calcium, copper,
iron,
manganese, magnesium, molybdenum, nickel, selenium or zinc. In another aspect,
the metal-containing compound is a metal oxide, a metal carbonate, a metal
hydroxide
or a mixture thereof of calcium, manganese, magnesium or zinc. In still
another
aspect, the metal-containing compound is a metal oxide of calcium, manganese,
magnesium or zinc. In yet another aspect, the metal-containing compound is a
metal
oxide of manganese or zinc.
[0031] Examples of the metal-containing compound may include, but are not
limited
to, calcium oxide, calcium hydroxide, calcium carbonate, zinc oxide, zinc
hydroxide,
zinc carbonate, boron trioxide, manganese oxide, magnesium hydroxide,
molybdenum
trioxide, magnesium oxide, magnesium hydroxide, copper (II) oxide, iron (III)
oxide,
selenium hydroxide, nickel oxide, nickel hydroxide, nickel carbonate and
mixtures
thereof.
[0032] The organic acid that is reacted with the metal-containing compound is
one
selected from a sulfonic acid, a carboxylic acid, a phosphoric acid, a boric
acid and a
mixture thereof. The number of carbon atoms for the particular organic acid is
not
limited so long as it has a sufficient number of carbon atoms to render the
micronutrient salt that is formed substantially oil soluble. Thus, the number
carbon
atoms of the organic acid will vary depending on the particular metal-
containing
compound and the particular organic acid used in forming the micronutrient
salt. In
some aspects, the number of carbon atoms of the organic acid may be less than
30, in
other aspects less than 20 carbon atoms, in still other aspects less than 15
carbon
atoms, while in still other aspects the number of carbon atoms may be less
than 10. In
a further aspect, the number of carbon atoms of the organic acid may be more
than 3,
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in other aspects more than 5 carbon atoms, in still other aspects more than 10
carbon
atoms, while in still other aspects it may be more than 15 carbon atoms. In
still
further aspects, the number of carbon atoms of the organic acid may range from
1 to
30, or from 4 to 25 or even from 8 to 15.
[0033] According to one aspect, the organic acid is a sulfonic acid. The
sulfonic acid
may be represented by the general formula
R1SO3H or (Ri)õArS03H
wherein R1 is a hydrocarbyl based group having less than 30 carbon atoms, and
can
be, for example, an aliphatic group such as alkyl, alkenyl, alkoxy,
alkoxyalkyl, or a
carboalkoxyalkyl group; x is an integer of 1 to 3; and, Ar is an aromatic
hydrocarbon
nucleus, including, but not limited to, a benzene or naphthalene nucleus. The
groups
Ar and R1 above can also contain other substituents such as hydroxy, mercapto,
halogen, nitro, amino, nitroso, carboxy and lower carboalkoxy as long as the
essential
hydrocarbon character of the Ar and R1 groups is not destroyed.
[0034] Examples of sulfonic acids include, but are not limited to, mahogany
sulfonic
acids, alkylated aromatic sulfonic acids, petrolatum sulfonic acids, mono- and
polywax-substituted naphthalene sulfonic acids, cetylchlorobenzene sulfonic
acids,
cetylphenol sulfonic acids, cetylphenol disulfide sulfonic acids, cetoxycapryl
benzene
sulfonic acids, dicetyl thianthrene sulfonic acids, di-lauryl beta-naphthol
sulfonic
acids, dicapryl nitronaphthylene sulfonic acids, paraffin wax sulfonic acids,
unsaturated paraffin wax sulfonic acids, hydroxy-substituted paraffin wax
sulfonic
acids, tetraisobutylene sulfonic acids, tetraamylene sulfonic acids, chloro-
substituted
paraffin wax, nitrosyl-substituted paraffin wax sulfonic acids, petroleum
naphthene
sulfonic acids, cetylcyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic
acids and
mono- and polywax-substituted cyclohexyl sulfonic acids.
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[0035] In another aspect, the organic acid is a carboxylic acid. The
carboxylic acid
may be a mono- or polycarboxylic acid (if the latter, it is generally a di- or
tricarboxylic acid). Monocarboxylic acids include C1 - C7 lower acids (for
e.g. acetic,
proprionic, butryric acid) and higher C8+ acids (for e.g., octanoic, decanoic,
etc.) as
well as known fatty acids having about 12-30 carbon atoms. The fatty acids are
often
mixtures of straight and branched chain acids containing, for example, from
about 5%
to about 30% (moles) straight chain acids and about 70% to about 95% (moles)
branched chain acids. Other commercially available fatty acid mixtures
containing
much higher proportions of straight chain acids are also useful. Mixtures
produced
from dimerization of unsaturated fatty acids can also be used.
[0036] In addition, dicarboxylic acids may include the well-known dicarboxylic
acids
made by alkylating maleic anhydride or its derivatives. The products of such
reactions are hydrocarbon substituted succinic acids, anhydrides, and the
like. Lower
molecular weight dicarboxylic acids, such as polymethylene bridged acids
(glutaric,
adipic, and the like), can also be used to make the substantially oil soluble
micronutrients salts of this disclosure. Non-exclusive examples of
tricarboxylic acids
include citric acid, isocitric acid, aconitic acid, propane-1,2,3-
tricarboxylic acid and
trimersic acid.
[0037] In yet another aspect the organic acid is a phosphorus acid. The
phosphorus
acid compounds, which contain phosphorus having a valence of 3 or 5 include:
(Ia)
R20
______________________________________ OH
n
Acid esters of phosphorus acid
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(Ib)
R20
P _____________________________________ OH
R30 ==7'-
0
Acid esters of phosphoric acid
(Ic)
R30
R20 _____________________________ P- OH
I
0
Acid esters of phosphonic acid
(Id)
OH
R20 _____________________________ P- OH
0
Phosphonic acid
(1e)
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_____________________________________ OH
R3
Phosphinic acids
(If)
OH
0 -1,- OH
OH
Phosphoric acid
(Ig)
OH
_________________________________ OH
OH
Phosphorus acid
(Ih)
0
1,=77 OH
P ________________________________ OH
OH
0
Metaphosphoric acid
(Ii)
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OH OH
OH- P-P-OH
H
0 0
Pyrophosphoric acid
wherein R2 and R3 are each, independently an aliphatic, aromatic or non-
aromatic
alicyclic hydrocarbon or heterocyclic radical having from 1 to 30 carbon
atoms.
[0038] Examples of phosphorus acids include, but are not limited to,
di(phenyl)
phosphite, monophenyl phosphite, mono-(diphenyl) phosphite, dicresyl
phosphite, di-
(oisooctylphenyl) phosphite, di(p-ethylhexlphenyl) phosphite, di(p-t-
octylphenyl)
phosphite, di(dimethylphenyl) phosphite, di-n-butyl phosphite, di-2-ethylhexyl
phosphite, mono-2-ethyl hexyl phosphite, diisooctyl phosphite, monoisooctyl
phosphite, monododecyl phosphite, 2-ethylhexyl phenyl phosphite, 2-ethylhexyl-
(n-
octylphenyl) phosphite, monocyclohexyl phosphite, dicyclohexyl phosphite, di(2-
cyclohexyl phenyl) phosphite, di-a-naphthyl phosphite, dipenyl phenyl
phosphite,
di(diphenyl) phospite, di-(2-phenyl ethyl) phosphite, dibenzyl phosphite,
monobenzyl
phosphite, n-butyl cresyl phosphite, didodecyl phosphite, ditetrahydrofurfuryl
phosphite, difuryl phosphite, diphenyl phosphate, monophenyl phosphate,
dicresyl
phosphate, di(dimetylphenyl) phosphate, di-n-butyl phosphate, di(p-t-
octylphenyl)
phosphate, di(o-t-octylphenyl) phosphate, di(2-ethylhexylphenyl) phosphate, di-
2-
ethylhexyl phosphate, mono-2-ethylhexyl phosphate, diisooctyl phosphate
monoisooctyl phosphate, monododecyl phosphate, 2-ethylhexyl phenyl phosphate,
2-
ethylhexyl-(p-t-octyl phenyl) phosphate, dicyclohexyl phosphate,
monocyclohexyl
phosphate, ditetrahydrofurfuryl phosphate, difuryl phosphate, di(2cyclohexyl
phenyl)
phosphate, di-a-naphthyl phosphate, di(diphenyl) phosphate, diphenyl phenyl
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phosphate, di(2-phenyl ethyl) phosphate, dibenzyl phosphate, monobenzyl
phosphate,
n-butyl cresyl phosphate, didodecyl phosphate, benzene phosphonic acid, 2-
ethylhexyl phosphonic acid, n-butyl phosphonic acid, isoamyl phosphonic acid,
cyclohexyl phosphonic acid, a-naphthyl phosphonic acid, benzyl phosphonic
acid, 2-
phenylethyl phosphonic acid, tolyl phosphonic acid, 2-cyclohexyl phenyl
phosphonic
acid and diphenyl phosphonic acid, phenyl ethyl acid phosphonate, 2-ethyl-
hexyl
phenyl acid phosphonate, di(2-ethylhexyl) acid phosphonate, cresyl tolylacid
phosphonate, di(phenyl) acid phosphonate, di(cyclohexyl) acid phosphonate,
di(tetrahydrofurfuryl) acid phosphonate, diphenyl phosphinic acid, di-2-
ethylhexyl
phosphinic acid, di(t-octylphenyl) phosphinic acid, 2- ethylhexyl phenyl
phosphinic
acid, isobuty1-2-ethylhexyl phosphinic acid, di-n-propyl phosphinic acid, di-a-
naphthyl phosphinic acid, dicyclohexyl phosphinic acid, ditolyl phosphinic
acid,
dibenzyl phosphinic acid, isooctyl benzyl phosphinic acid, di(2-phenyl ethyl)
phosphinic acid, diphenyl phenyl phosphinic acid, di(diphenyl) phosphinic
acid, 2-
etylhexyl (t-octyl phenyl) phosphinic acid and di(dimethylphenyl) phosphinic
acid.
[0039] In another aspect, the organic acid is a boric acid. The boric acid may
be any
of the various forms of boric acid, including metaboric acid (HB02),
orthoboric acid
(H3B03) and tetraboric acid (H2B407). The boric acid may also be an ester of
these
acids including, for example, the methyl, ethyl and propyl esters, with the
methyl
esters being most readily available and therefore most often used.
[0040] The substantially oil soluble micronutrient salt may be obtained by
reacting
the metal-containing compound and organic acid in an organic solvent. After
the
reaction is complete, the organic solvent may be removed so that the
substantially oil
soluble micronutrient salt is isolated.
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[0041] The reaction between the organic acid and metal-containing compound may
be
carried out by using 2 to 3 moles, or using 2 to 2.5 moles, or even using 1.5
moles to 2
moles of the organic acid with respect to 1 mole of the metal-containing
compound.
[0042] Organic solvents that can be used include a hydrocarbon solvent, an
alcohol
solvent, an ester solvent, or an ether solvent. Examples of the hydrocarbon
solvent
include n-hexane, n-octane, cyclohexane, toluene, and xylene. Examples of the
alcohol solvent include methanol, ethanol, propanol, butanol, ethylene glycol,
and
propylene glycol. Examples of the ester solvent include ethyl acetate, butyl
acetate,
ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl
ether
acetate. Examples of the ether solvent include ethylene glycol monomethyl
ether,
ethylene glycol monoethyl ether, and propylene glycol monomethyl ether. These
solvents can be used alone or in combination of two or more.
[0043] The reaction between the metal-containing compound and organic acid may
occur at any suitable temperatures, such as at a temperature between 40 C to
95 C, or
at a temperature between 40 C to 90 C, or even at a temperature between 40 C
to
80 C.
[0044] Once the reaction is complete, the solvent can be removed at a
temperature of
80 C or less, or at a temperature of 70 C or less, or even at a temperature of
60 C or
less. The solvent can be removed by methods commonly used by those skilled in
the
art. For example, such methods include drying under reduced pressure,
lyophilization, spray drying, or air blow drying. It is preferable in one
aspect that
solvent removal is performed in a time that is as short as possible.
[0045] The adjuvant composition also includes an oil. In one or more aspects,
the oil
may be a vegetable oil, a mineral oil, a paraffin oil, a fatty acid ester or a
mixture
thereof.
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[0046] According to one aspect, the oil is a vegetable oil. Examples of
vegetable oils
include, but are not limited to, soybean oil, coconut oil, palm oil, cotton
seed oil,
wheat germ oil, olive oil, corn oil, sunflower oil, safflower oil, rapeseed
oil, mustard
oil, tallow, palmitate, stearate, oleate, linoleate, soybean oil methyl ester,
soybean oil
ethyl ester, soybean oil propyl ester, coconut oil methyl ester, coconut oil
ethyl ester,
coconut oil propyl ester, palm oil methyl ester, palm oil ethyl ester, palm
oil propyl
ester, cotton seed oil methyl ester, cotton seed oil ethyl ester, cotton seed
oil propyl
ester, wheat germ methyl ester, wheat germ ethyl ester, wheat germ propyl
ester, olive
oil methyl ester, olive oil ethyl ester, olive oil propyl ester, corn oil
methyl ester, corn
oil ethyl ester, corn oil propyl ester, sunflower oil methyl ester, sunflower
oil ethyl
ester, sunflower oil propyl ester, safflower oil methyl ester, safflower oil
ethyl ester,
safflower oil propyl ester, rapeseed oil methyl ester (biodiesel), rapeseed
oil ethyl
ester, rapeseed oil propyl ester, mustard oil methyl ester, mustard oil ethyl
ester,
mustard oil propyl ester, jatropha methyl ester, jatropha ethyl ester,
jatropha propyl
ester, tallow methyl ester, tallow ethyl ester, tallow propyl ester, methyl
palmitate,
ethyl palmitate and propyl palmitate.
[0047] In another aspect, the oil is a mineral oil. Suitable mineral oils
generally
include various commercially available distillate fractions of mineral oil
(petroleum).
In one aspect, preference is given to mixtures of open-chain C14-C30
hydrocarbons,
cyclic hydrocarbons (naphthenes) and aromatic hydrocarbons. The hydrocarbons
can
be either straight-chain or branched. In another aspect, particular preference
is given
to mixtures having an aromatic portion of less than 8% by weight or even
mixtures
having an aromatic portion of less than 4% by weight.
[0048] In still another aspect, the oil is a paraffin oil. Examples of such
paraffin oils
are straight-chain and branched C14-C30 hydrocarbons. Paraffin oils are also
known as
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base oil or white oil and are commercially available, for example, under the
Bayol0
and Marcol0 brand oils, BAR 0020 oil, Pionier 0032-20 oil or, Kristol M14 oil.
[0049] In a further aspect, the oil is a fatty acid ester. Suitable fatty acid
esters
generally include alkyl fatty acid esters, such as Ci-C20 alkyl Cio-C22 fatty
acid esters.
In one aspect, preference is given to methyl esters, ethyl esters, propyl
esters, butyl
esters, 2-ethylhexyl esters and dodecyl esters and mixtures thereof In another
aspect,
particular preference is given to methyl esters and ethyl esters. Examples of
synthetic
fatty acid esters are, for example, those which are derived from fatty acids
having an
odd number of carbon atoms, such as CI i-C21-fatty acid esters.
[0050] In another aspect, the adjuvant composition may contain a surfactant.
Surfactants are surface-active compounds, such as anionic, cationic, nonionic
and
amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof
Such
surfactants can be used as an emulsifier, dispersant, solubilizer, wetter,
penetration
enhancer or protective colloid. Examples of surfactants useful in the present
disclosure are listed in McCutcheon's, Vold : Emulsifiers & Detergents,
McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North
American Ed.), the contents of which is herein incorporated by reference.
[0051] Anionic surfactants may include alkali, alkaline earth or ammonium
salts of
sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof Examples
of
sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin
sulfonates, lignin
sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated
alkylphenols,
sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes,
sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and
alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates
are
sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of
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ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are
phosphate
esters. Examples of carboxylates are alkyl carboxylates, and carboxylated
alcohol or
alkylphenol ethoxylates.
[0052] Nonionic surfactants may include alkoxylates, N-substituted fatty acid
amides,
amine oxides, esters, sugar-based surfactants, polymeric surfactants, and
mixtures
thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols,
amines, amides, arylphenols, fatty acids or fatty acid esters which have been
alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide
may be
employed for the alkoxylation, preferably ethylene oxide. Examples of N-
substituted
fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
Examples of
esters are fatty acid esters, glycerol esters or monoglycerides. Examples of
sugar-
based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose
esters.
Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone,
vinylalcohols, or vinylacetate.
[0053] Cationic surfactants may include quaternary surfactants, for example
quaternary ammonium compounds with one or two hydrophobic groups, or salts of
long-chain primary amines. Suitable amphoteric surfactants are alkylbetains
and
imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A
type
comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-
C
type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable
polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali
salts of
polyacrylic acid or polyacid comb polymers. Examples of polybases are
polyvinylamines or polyethyleneamines.
[0054] The adjuvant composition may also contain an auxiliary component.
Examples of auxiliary components include, but are not limited to, emulsifiers,
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solvents, liquid carriers, solid carriers or fillers, dispersants, wetters,
adjuvants,
solubilizers, penetration enhancers, protective colloids, adhesion agents,
thickeners,
humectants, repellents, attractants, feeding stimulants, compatibilizers,
bactericides,
anti-freezing agents, crystallization inhibitors, anti-foaming agents,
colorants,
tackifiers, binders, preservatives, inorganic or organic acids to neutralize
the pH,
clarifiers, stabilizers, fertilizers, such as ammonium sulfate, urea or
compound
fertilizers, for example phosphorus-, potash- and nitrogen-based compound
fertilizers,
such as P,K,N fertilizers, UV stabilizers and mixtures thereof.
[0055] Examples of emulsifiers which may be used are calcium salts of
alkylarylsulfonic acid, such as calcium dodecylbenzenesulfonate, or nonionic
emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers,
fatty
alcohol polyglycol ethers, propylene oxidelethylene oxide condensates, alkyl
polyethers, sorbitan esters such as, for example, sorbitan fatty acid esters,
or
polyoxyethylene sorbitan esters such as, for example, polyoxyethylene sorbitan
fatty
acid esters.
[0056] Solvents and liquid carriers can be water and organic solvents, such as
aliphatic, cyclic and aromatic hydrocarbons, for e.g. toluene, paraffin,
tetrahydronaphthalene, alkylated naphthalenes; alcohols, for e.g. ethanol,
propanol,
butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, for e.g.
cyclohexanone; esters, for e.g. lactates, carbonates, fatty acid esters, gamma-
butyrolactone; fatty acids; phosphonates; amines; amides, for e.g. N-
methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof. In one
aspect,
the solvent is an organic solvent.
[0057] Crystallization inhibitors can be polyacrylic acids and their salts,
whereas the
latter are preferred. The salts of polyacrylic acids may be ammonium, primary,
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secondary or tertiary ammonium derivatives, or alkali metal salts (e.g.
sodium,
potassium, lithium ions), wherein alkali metal salts such as sodium salts are
preferred
in one aspect. The polyacrylic acids and their salts usually have a molecular
weight
(as detennined by GPC, calibration with polystyrene sulphonates) of 1000 Da to
300
kDa, alternatively of 1000 Da to 80 kDa, and in particular 1000 Da to 15 kDa.
The
crystallization inhibitors are usually water-soluble, for e.g. at least 1 g/1,
alternatively
at least 10 g/1, and in particular at least 100 g/1 at 20 C.
[0058] Solid carriers or fillers can be mineral earths, for e.g. silicates,
silica gels, talc,
kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth,
bentonite,
polysaccharide powders, for e.g. cellulose, starch, products of vegetable
origin, for
e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures
thereof.
[0059] Thickeners include polysaccharides (for e.g.,
xanthan gum,
carboxymethylcellulose), organic clays (organically modified or unmodified),
polycarboxylates, and silicates.
[0060] Bactericides include bronopol and isothiazolinone derivatives such as
alkylisothiazolinones and benzisothiazolinones.
[0061] Anti-freezing agents include ethylene glycol, propylene glycol and
glycerin.
[0062] Anti-foaming agents include silicones, long chain alcohols, and salts
of fatty
acids. Preferred anti-foaming agents are silicones, such as
polydimethylsiloxane.
[0063] Colorants (for e.g., in red, blue, or green) include pigments of low
water
solubility and water-soluble dyes. Examples are inorganic colorants (for e.g.,
iron
oxide, titan oxide, iron hexacyanoferrate) and organic colorants (for e.g.,
alizarin-,
azo- and phthalocyanine colorants).
[0064] Tackifiers or binders include polyvinylpyrrolidone, polyvinylacetates,
polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and
cellulose ethers.
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[0065] Anti-drift agents are, for example, nonionic polymers, such as
polyacrylamides, polyethylene glycols, or guar gum with a molecular weight of
at
least 20 kDa, preferably at least 50 kDa, and in particular at least 100 kDa.
Further
examples for anti-drift agents are lecithin and self emulsifiable polyesters.
[0066] Humectants are typically compounds, which attract and/or keep water
within
the adjuvant composition. Examples include glycerol or sugar syrups.
[0067] In one exemplary aspect, the adjuvant composition comprises (a) 0.01%
by
weight to 20% by weight of the substantially oil soluble micronutrient salt of
the
present disclosure and (b) 0.01% by weight to 45% by weight of the oil, where
the %
by weight is based on the total weight of the adjuvant composition. In another
exemplary aspect, the adjuvant composition comprises (a) 0.5% by weight to 15%
by
weight of the substantially oil soluble micronutrient salt of the present
disclosure and
(b) 1% by weight to 35% by weight of the oil, where the % by weight is based
on the
total weight of the adjuvant composition. In still another exemplary aspect,
the
adjuvant composition comprises (a) 1% by weight to 10% by weight of the
substantially oil soluble micronutrient salt of the present disclosure and (b)
5% by
weight to 30% by weight of the oil, where the % by weight is based on the
total
weight of the adjuvant composition.
[0068] In another exemplary aspect, the adjuvant composition comprises (a)
0.01%
by weight to 20% by weight of the substantially oil soluble micronutrient salt
of the
present disclosure (b) 0.01% by weight to 45% by weight of the oil and (c)
0.1% by
weight to 25% by weight of the surfactant, where the % by weight is based on
the
total weight of the adjuvant composition. In still another exemplary aspect,
the
adjuvant composition comprises (a) 0.5% by weight to 15% by weight of the
substantially oil soluble micronutrient salt of the present disclosure (b) 1%
by weight
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to 35% by weight of the oil, and (c) 0.5% by weight to 20% by weight of the
surfactant, where the % by weight is based on the total weight of the adjuvant
composition. In yet another exemplary aspect, the adjuvant composition
comprises
(a) 1% by weight to 10% by weight of the substantially oil soluble
micronutrient salt
of the present disclosure (b) 5% by weight to 30% by weight of the oil and (c)
1% by
weight to 15% by weight of the surfactant, where the % by weight is based on
the
total weight of the adjuvant composition.
[0069] In yet another exemplary aspect, the adjuvant composition comprises (a)
0.01% by weight to 20% by weight of the substantially oil soluble
micronutrient salt
of the present disclosure (b) 0.01% by weight to 45% by weight of the oil, (c)
0.1% by
weight to 25% by weight of the surfactant and (d) 0.1% by weight to 90% by
weight
of an auxiliary component, where the % by weight is based on the total weight
of the
adjuvant composition. In another exemplary aspect, the adjuvant composition
comprises (a) 0.5% by weight to 15% by weight of the substantially oil soluble
micronutrient salt of the present disclosure (b) 1% by weight to 35% by weight
of the
oil, (c) 0.5% by weight to 20% by weight of the surfactant and (d) 1% by
weight to
50% by weight of an auxiliary component, where the % by weight is based on the
total weight of the adjuvant composition.
[0070] The adjuvant compositions of the present disclosure can be easily be
prepared
in any suitable vessel or container. The order of mixing the components is not
particularly important and generally the various components can be added
sequentially or all at once. Thus, the aqueous compositions may be prepared by
combining: (i) the substantially oil soluble micronutrient salt with (ii) the
oil and
optionally (iii) surfactant and optionally (iv) auxiliary component(s). Each
of the
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above may be combined at any suitable temperature such as at temperatures
ranging
from 10 C to 70 C.
[0071] Once formulated, the adjuvant compositions may be packaged in a variety
of
containers such as steel, tin, or aluminum cans, plastic or glass bottles and
paper or
cardboard containers.
[0072] In a further aspect, there is provided an agrochemical formulation
comprising
the adjuvant composition of the present disclosure and a pesticide (and
auxiliary
component(s) in aspects where such auxiliary component(s) are present in the
agrochemical formulation and were not included in formulating the adjuvant
composition). The agrochemical formulation may be used in treating target
substrates
such as those disclosed above and refers to all forms of compositions
including
concentrates and spray formulations. "Spray formulations" are aqueous
agrochemical
formulations that include all of the components to be applied to the target
substrate or
their environment in a form and at a concentration (dilution) that is
appropriate for
spraying. Spray formulations can be made up by simple dilution of concentrates
containing desired components, by mixing the individual components, or a
combination of diluting a concentrate and adding further individual components
or
mixtures of components. Typically such end use mixing is carried out in the
spray
tank from which the formulation is sprayed or a holding tank for filling the
spray tank
and commonly such mixing and mixtures are called tank mixing and tank
mixtures.
"Concentrates" are agrochemical formulations, which may be aqueous or non-
aqueous, and which are designed to be diluted with water (or a water-based
liquid) to
form the corresponding spray formulations and include such compositions in
liquid
form such as solutions, emulsions or dispersions and in solid form, especially
in water
dispersible solid form, such as granules or powders. The agrochemical
formulations
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according to the present disclosure may be prepared by customary processes,
for
example by mixing, by grinding, dissolving or dispersing the individual
components,
preferably at room temperature or ambient conditions. If other formulation
auxiliary
components are present, they are likewise incorporated at room temperature or
ambient conditions. In general, the sequence in which the individual
components are
added is of no decisive importance. Thus, in one aspect the adjuvant
composition
disclosed above may be formulated in a container, for example, in a stainless
steel
tank, steel, tin, aluminum can, plastic or glass bottle and paper or cardboard
container.
The adjuvant composition may then be combined with a pesticide and water
and/or
other solvent, and in some aspects an auxiliary component, to form an
agrochemical
formulation in the field just prior to application.
[0073] The presently described adjuvant composition is not limited for use
with any
particular class of pesticides. In some particular aspects, the adjuvant
composition is
used in connection with water soluble pesticides, such as glyphosate, 2,4-D,
dicamba
and glufosinate.
[0074] In one aspect, the pesticide includes any chemical or biological agent
(i.e.
"active ingredient") used in preventing, destroying, repelling, or mitigating
a pest.
Thus, in one particular aspect, the pesticide is a fungicide, herbicide,
insecticide,
algaecide, molluscicide, miticide, rodenticide, growth regulator or insect
repellant.
[0075] According to one aspect, the pesticide is a fungicide. Examples of
fungicides
include, but are not limited to: azoxystrobin, trifloxystrobin, kresoxim
methyl,
famoxadone, metominostrobin and picoxystrobin, carbendazim, thiabendazole,
dimethomorph, vinclozolin, iprodione, dithiocarbamate, imazalil, prochloraz,
fluquinconazole, epoxiconazole, flutriafol, azaconazole, bitertanol,
bromuconazole,
cyproconazole, difeno conazo le, hexaconazole, paclobutrazole, prop iconazole,
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tebuconazole, triadimefon, trtiticonazole, fenpropimorph, tridemorph,
fenpropidin,
mancozeb, metiram, chlorothalonil, thiram, ziram, captafol, captan, folpet,
fluazinam,
flutolanil, carboxin, metalaxyl, bupirimate, ethirimol, dimoxystrobin,
fluoxastrobin,
orysastrobin, metominostrobin,
prothioconazole, 8-(2,6-diethy1-4-methyl-
phenyl)tetrahydropyrazolo[1,2-d][1,4,5]oxadiazepine-7,9-dione, 2,2,-
dimethyl-
propionic acid-8-
(2,6- diethy1-4-methyl-pheny1)-9-oxo -1,2,4,5 -tetrahydro-9H-
pyrazolo-[1,2 d][1,4,5]oxadiazepine-7-y1 ester and metalaxyl.
[0076] In another aspect, the pesticide is a herbicide. Examples of herbicides
include,
but are not limited to: fluzifop, mesotrione, fomesafen, tralkoxydim,
napropamide,
amitraz, propanil, cyprodanil, pyrimethanil, dicloran, tecnazene, toclofos
methyl,
flamprop M, 2,4-D, MCPA, mecoprop, clodinafop-propargyl, cyhalofop-butyl,
diclofop methyl, haloxyfop, quizalofop-P, indo1-3-ylacetic acid, 1-
naphthylacetic
acid, isoxaben, tebutam, chlorthal dimethyl, benomyl, benfuresate, dicamba,
dichlobenil, benazolin, triazoxide, fluazuron, teflubenzuron, phenmedipham,
acetochlor, alachlor, metolachlor, pretilachlor, thenylchlor, alloxydim,
butroxydim,
clethodim, cyclodim, sethoxydim, tepraloxydim, pendimethalin, dinoterb,
bifenox,
oxyfluorfen, acifluorfen, fluoroglycofen-ethyl, bromoxynil, ioxynil,
imazamethabenz-
methyl, imazapyr, imazaquin, imazethapyr, imazapic, imazamox, flumioxazin,
flumiclorac-pentyl, picloram, amodosulfuron, chlorsulfuron, nicosulfuron,
rimsulfuron, triasulfuron, triallate, pebulate, prosulfocarb, molinate,
atrazine,
simazine, cyanazine, ametryn, prometryn, terbuthylazine, terbutryn,
sulcotrione,
isoproturon, linuron, fenuron, chlorotoluron, metoxuron, N-
phosphonomethylglycine
and its salts (glyphosate), glufosinate, chlormequat chloride, paraquat,
diquat,
trifloxysulfuron, fomesafen, mesotrione and fenuron.
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[0077] In yet another aspect, the pesticide is an insecticide. Examples of
insecticides
include, but are not limited to: abamectin, acephate, acetamiprid,
acrinathrin,
alanycarb, aldicarb, allethrin, alpha-cypermethrin, amitraz, asulam,
azadirachtin,
azamethiphos, azinphos-ethyl, azinphos-methyl, bendiocarb, benfuracarb,
bensultap,
beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioresmethrin,
bistrifluron, borax, buprofezin, butoxycarboxim, cadusafos, carbaryl,
carbofuran,
chlorpropham, clothianidin, cyfluthrin, cyhalothrin, cyprmethrin,
deltamethrin,
diethofencarb, diflubenzuron, dinotefuran, emamectin, endosulfan, fenoxycarb,
fenthion, fenvalerate, fipronil, halfenprox, heptachlor, hydramethylnon,
imidacloprid,
imiprothrin, isoprocarb, lambda cyhalothrin, methamidophos, methiocarb,
methomyl,
nitenpyram, omethoate, permethrin, pirimicarb, pirimiphos methyl, propoxur,
tebufenozide, thiamethoxam, thiodicarb, triflumoron, and xylylcarb.
[0078] In still another aspect, the pesticide is an algaecide. Examples of
algaecides
include, but are not limited to: bethoxazin, copper dioctanoate, copper
sulfate,
cybutryne, dichlone, dichlorophen, endothal, fentin, hydrated lime, nabam,
quinoclamine, quinonamid, simazine, triphenyltin acetate, and triphenyltin
hydroxide.
[0079] In a further aspect, the pesticide is a molluscicide. Examples of
moluscicides
include, but are not limited to: metaldehyde, methiocarb and aluminium
sulfate.
[0080] In still a further aspect, the pesticide is a miticide. Examples of
miticides
include, but are not limited to: antibiotic miticides, carbamate miticides,
formamidine
miticides, mite growth regulators, organochlorine, permethrin and
organophosphate
miticides.
[0081] In an additional aspect, the pesticide is a rodenticide. Examples of
rodenticides include, but are not limited to: 2-isovalerylindan-1, 3-dione, 4-
(quinoxalin-2-ylamino)benzenesulfonamide, alpha-
chlorohydrin, aluminium
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phosphines, anta, arsenics oxide, barium carbonate, bisthiosemi, brodifacoum,
bromadiolone, bromethalin, calcium cyanide, chloralose, chlorophacinone,
cholecalciferol, coumachlor, coumafuryl, coumatetralyl, crimidine, difenacoum,
difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide,
flupropadine, flupropadine hydrochloride, gamma-HCH, HCH, hydrogen cyanide,
iodomethane, lindane, magnesium phosphide, methyl bromide, norbormide,
phosacetim, phosphine, phosphorus, pindone, potassium arsenite, pyrinuron,
scilliroside, sodium arsenite, sodium cyanide, sodium fluoroacetate,
strychnine,
thallium sulfate, warfarin, and zinc phosphide.
[0082] In still another aspect, the pesticide is a growth regulator. Examples
include,
but are not limited to, abscisic acid, amidochlor, ancymidol, 6-
benzylaminopurine,
brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride,
cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine,
ethephon,
flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid,
inabenfide,
indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat
chloride),
naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione
(prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl
phosphorotrithioate, 2,3,5-tri-iodobenzoic acid, trinexapac-ethyl and
uniconazole.
[0083] According to another aspect, the pesticide is an insect repellant.
Examples of
insect repellants, include, but are not limited to: 2-ethyl-1,3-hexanediol; N-
octyl
bicycloheptene dicarboximide; N,N-diethyl-M-toluamide; 2,3:4,5-Bis (2-
butylene)
tetrahydro-2-furaldehyde; Di-n-propyl isocinchomeronate; and 2-hydroxyethyl-n-
octyl sulfide.
[0084] In a particular aspect, the pesticide is a water-soluble herbicide. The
term
"water-soluble" as used herein in relation to a herbicide or salt thereof
means having a
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solubility in deionized water at 20 C of not less than about 200 g/l. In some
aspects,
the water-soluble herbicides have a herbicidal active acid or anionic moiety
and are
most usefully present in the form of one or more water-soluble salts. The
aqueous
phase can optionally contain, in addition to the water-soluble herbicide,
other salts
contributing to the ionic strength of the aqueous phase. In one particular
aspect, the
agrochemical formulation includes a water-soluble herbicide and the adjuvant
composition of the present disclosure.
[0085] Water-soluble herbicides include acifluorfen, acrolein, amitrole,
asulam,
benazolin, bentazon, bialaphos, bromacil, bromoxynil, chloramben, chloroacetic
acid,
clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, difenzoquat, diquat,
endothall, fenac, fenoxaprop, flamprop, flumiclorac, fluoroglycofen,
flupropanate,
fomesafen, fosamine, glufosinate, glyphosate, imazameth, imazamethabenz,
imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB,
mecoprop, methylarsonic acid, naptalam, nonanoic acid, paraquat, picloram,
quinclorac, sulfamic acid, 2,3,6-TBA, TCA, triclopyr and water-soluble salts
thereof.
[0086] The amount of pesticide included in the agrochemical formulation of the
present disclosure will vary according to a number of parameters such as the
target
substrate to be treated, the area to be treated, etc. In general, a rate of
application
from about five grams to about four kilograms per hectare (g/ha) of pesticide
may be
suitable in some aspects.
[0087] The agrochemical formulations of the present disclosure may be used in
conventional agricultural methods. For example, the pesticide and adjuvant
composition may be mixed with water if desired and applied post-emergence to a
desired target substrate by any means, such as airplane spray tanks, knapsack
spray
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tanks, cattle dipping vats, farm equipment used in ground spraying (e.g., boom
sprayers, hand sprayers), and the like.
[0088] As discussed above, in accordance with some aspects, the agrochemical
formulation can be a concentrate composition, which can be diluted in a
suitable
volume of water to form a spray formulation (e.g., a tank mix composition) for
applying to the target substrate. The concentrate composition can be in
liquid, solid,
or semi-solid form.
[0089] In one aspect, the amount of the pesticide in the concentrate
composition can
range from about 1% by weight to about 80% by weight, alternatively from about
16% by weight to about 60% by weight, alternatively from 35% by weight to
about
55% by weight, based on the total weight of the concentrate composition. The
amount of the adjuvant composition in the concentrate composition may range
from
about 0.0001% by weight to about 30% by weight, alternatively between from
about
0.001% by weight to about 20% by weight, or alternatively from about 0.01% by
weight to about 10% by weight percent, or alternatively from about 0.1% by
weight to
about 5% by weight, or even alternatively from about 0.5% by weight to about
3% by
weight, based on the total weight of the concentrate composition.
[0090] The concentrate composition can be diluted by a user with water to
render a
spray formulation containing from about 0.01% by weight to about 15% by
weight,
alternatively from about 0.1% by weight to about 5% by weight, alternatively
from
about 0.2% by weight to about 2% by weight of the pesticide, based on the
total
weight of the spray formulation. The spray formulation can typically contain
from
about 0.0001% by weight to about 6% by weight, alternatively from about 0.001%
by
weight to about 5% by weight, alternatively from about 0.01% by weight to
about 4%
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by weight percent of the adjuvant composition of the present disclosure, based
on the
total weight of the spray formulation.
[0091] In still other aspects of the present disclosure, the pesticide and
adjuvant
composition are combined to form a "ready-to-use" (RTU) spray formulation. The
RTU spray formulation can be prepared by a user by diluting a concentrate
composition as described above, or alternatively can be provided to the user
as is. For
example, the RTU spray formulation can contain from about 0.5% by weight to
about
5% by weight, alternatively from about 0.75% by weight to about 3% by weight,
alternatively from about 1.5% by weight to about 2.5% by weight of the
pesticide,
based on the total weight of the RTU spray formulation. The RTU spray
formulation
can also contain from about 0.01% by weight to about 5% by weight,
alternatively
from about 0.2% by weight to about 3% by weight, alternatively from about 0.5%
by
weight to about 2% by weight of the adjuvant composition of the present
disclosure.
The balance of the RTU composition can be water.
[0092] In accordance with another aspect, the presently described technology
provides a method for killing or inhibiting or repelling a pest comprising the
steps of
providing a pesticide in a pesticidally effective amount, providing the
adjuvant
composition of the present disclosure, combining the pesticide with the
adjuvant
composition to prepare an agrochemical formulation, and contacting the
agrochemical
formulation and the pest.
Examples
[0093] Example 1. Zinc salt of linear alkylbenzene sulfonate
The zinc salt of linear alkylbenzene sulfonic acid (LAS) was made by reacting
300 g
of LAS with 36 g of ZnO in the presence of 300 g of methanol at 70 C for 4
hours.
To this mixture was then added 100 g of TERMUL05500 product (a butyl initiated
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EO/PO block polymer), 100 g of propylene glycol butyl ether (PGBE), and 50 g
of
methylated soybean oil (MSO). This mixture was stirred under reduced pressure
and
heated to 70 C until all of the methanol was removed. The resulting viscous
orange
liquid contained 5% Zn metal and formed microemulsions when diluted into hard,
medium, and soft waters.
[0094] Example 2. Zinc 2-Ethylhexylphosphate ester
Methanol (245 g) was added to a round bottom flask equipped with a stir bar,
and 332
g of the phosphate ester of 2-ethylhexanol was added and the solution was
stirred until
homogeneous. ZnO (31 g) was then added and the mixture was heated to 70 C and
stirred for 4 hours. The methanol was removed under reduced pressure and 73 g
MSO was added along with 24 g SURFONIC8 T-5 product (alkylamine ethoxylate),
20 g TERMULO 3150 emulsifier, and 20 g TERMUL8 5500 product. The resulting
viscous yellow liquid formed microemulsions when diluted into hard, medium,
and
soft waters.
[0095] Example 3. Zinc/Manganese LAS
A mixed Zn and Mn salt of LAS was produced in this example. 842.3 g LAS was
dissolved into 640 g methanol and 48.7 g ZnO and 50.5 g Mn0 were added slowly
and the mixture was stirred and heated to 70 C for 6 hours. 15 g of
triethanolamine
(TEA) was then added and methanol was removed under reduced pressure. Then,
140
g PGBE, 70 g MSO, and 112 g TERMULO 5500 were mixed in to give the final
product which contained 4.5% total metals. This product formed microemulsions
when diluted into hard, medium, and soft waters.
[0096] Example 4. Zinc/Manganese-Cumene sulfonic acid
300 g of cumene sulfonic acid and 300 g methanol were added to a round-bottom
flask equipped with a reflux condenser, stir bar, and thermocouple. 28 g ZnO
and 28
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g MnO were then added slowly and the mixture was stirred and heated to 70 C
for 6
hours. 5 g TEA was then added and the methanol removed under reduced pressure.
Then, 200 g water, 40 g SURFONICO CO-36 surfactant, 44 g tall oil fatty acid
(TOFA), and 100 g PGBE were added to form a transparent orange liquid that
formed
transparent microemulsions when diluted into hard, medium, and soft waters.
[0097] Example 5. Herbicide activity in micronutrients
Various herbicides and micronutrient fertilizers were tested for compatibility
along
with the Zn/Mn-LAS product from Example 3. Fertilizers were added to 342 ppm
(WHO) water at room temperature at recommended mix rates and herbicides were
mixed in at their own recommended rates. The samples were stored at room
temperature for 24 hours and then examined for any modes of failure (Possible
failure
modes include crystallization, flocculation, phase separation, etc.) The
compatibility
results are below in Table 1:
Table 1
Fertilizers
Nulex Zn/Mn-
9% Zn Nulex Chelate liquid Zinc Corn TJ LAS
Herbicide EDTA 10XL 20 Mix LS Micromix (Ex. 3)
Flexstar GT
(fomesafen +
glyphosate) Pass Pass Flocculates Pass Pass Pass
Clarity (Dicamba) Pass Flocculates Flocculates Pass Pass
Pass
Surpass
(acetochlor) Pass Flocculates Flocculates Pass Pass Pass
Powerline Floccul Floccula
(imazapyr) ates Flocculates Flocculates tes Pass Pass
Roundup
PowerMax
(glyphosate) Pass Pass Pass Pass Pass Pass
All comparative fertilizers that passed were clear solutions after storage for
24 hrs and
the ones that did not pass failed due to the appearance of flocculated
material. The
Zn/Mn-LAS product was compatible with all herbicides and produced stable
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microemulsions in each scenario, showing its usefulness as a tank-mix partner
for
herbicides.
[0098] Example 6. Zinc uptake measurements in corn seedlings
In this example, the Zn salt of linear alkylbenzene sulfonate from example 1
was
sprayed on corn seedlings that were grown in potting soil and zinc uptake into
the
plant leaves was measured and compared to uptake of other forms of zinc as
described
below. The samples that were analyzed were prepared by spraying the leaves
with the
particular formulation, drying the leaves after spraying, grinding the leaves,
digesting
them in aqua regia and measuring the concentration of zinc in solution by
inductively
coupled plasma mass spectrometry (ICP-MS). Spray treatment formulations were
prepared as follows, based on an average delivery of 3.3 mL solution per 4
inch
square pot (16 in2 treated area):
a) deionized water only
b) Ca-LAS/MSO: 1.07 g/L in deionized water
c) ZnSO4: 1.02 g/L ZnSO4 in deionized water to approximate the recommended
use rate of 1 lb Zn in 20 gallons solution per acre
d) Zn-LAS/MSO (5% w/w Zn, density 1.02 g/mL): 1.07 g/L in deionized water
to approximate a use rate of 0.15 lb Zn in 20 gallons solution per acre
e) Zn-EDTA (9% w/w Zn, density 1.31 g/mL): 0.59 g/L in deionized water to
approximate the recommended use rate of 0.15 lb Zn in 20 gallons solution per
acre.
After 48 hours of incubation, each seedling was cut just above the soil line
and the
aerial tissue was used for analysis. Seedlings were submerged in a series of
three
deionized water baths and agitated for 10 seconds. All three wash waters were
changed after each 8-10 seedlings and between treatment cohorts. Washed tissue
was
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placed in a clean, dry wide-mouth glass jar and incubated for 4-6 days at 40 C
until
dry. Dried tissue was ground with a mortar and pestle to a coarse powder. The
results are provided below in Table 2.
Table 2
Spray Formulation Relative Zinc Concentration
Water 1.0
Ca-LAS/MSO 0.95
ZnSO4 2.01
Zn-LAS/MS 0 1.82
Zn-EDTA 1.05
The data above was normalized to the water control (set as 1) and represents
the
average of two separate trials. The results show that the plants sprayed with
the
formulation from inventive example 1 contained almost twice as much zinc as
those
sprayed with Zn-EDTA (at the same rate of zinc) and a slightly lower amount of
zinc
than plants sprayed with ZnSO4(at a 6X higher rate of Zn). However, because
ZnSO4
was sprayed at a rate of 1.0 lb/acre while inventive example 1 was sprayed at
0.15
lb/acre, there was a much greater efficiency of zinc uptake with the inventive
formulation.
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[0099] Although making and using various aspects of the present invention have
been
described in detail above, it should be appreciated that the present invention
provides
many applicable inventive concepts that can be embodied in a wide variety of
specific
contexts. The specific aspects discussed herein are merely illustrative of
specific
ways to make and use the invention, and do not delimit the scope of the
invention.
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